Polyazo-dyestuffs



Patented Nov. 15, 1949 UNITED STATES PATENT QFFICE POLYAZO-DYESTUFFS No Drawing. Application March 27, 1945, Serial No. 585,188. In Switzerland May 25, 1944 5 Claims.

It has been found that new valuable polyazo dyestufis are obtained by converting primary disazo dyestuffs of the general formula OH NH;

wherein one X means a sulfonic acid group and the other X means hydrogen, Y means a sulfonic acid group or hydrogen and An and Arz represent aromatic radicals, which contain at least one group forming metal-complex compounds and each of which contains a radical Z which is capable of conversion into a diazotisable amino group, into diamino-disazo dyestufis, tetrazotising the same and combining the resulting tetrazonium compounds with two molecules of the same or different end components which are capable of coupling once and contain hydroxyl groups and which may also contain azo groups.

The same dyestuffs may also be prepared by first converting into an amino group one of the radicals Z which are present in the primary disazo dyestufis of the above formula, in which one Z means a nitro group and the other Z represents an acylamino group, diazotising the obtained amino group, coupling the resulting diazodisazo compound with one of the above-defined final components and subsequently converting the other radical Z into the amino group, carrying out a further diazotation and combining the so-obtained diazonium compound with the same or with another defined end component.

As metal-complex forming group in ortho-poe sition to the azo group or to Z in the above formula may be mentioned: carboxyl groups, a1-

hydroxyl groups.

As end components containing hydroxyl groups and. being capable of coupling only once may be used: derivatives of eeketocarboxylic acid esters, l ke l-phenyl-3-alkyl-, -arylor -carboxy- 5- pyrazolones, or fi-ketocarboxylic acid anilides and their substitution products, salicylic acids and their homologues which are capable of coupling, 1-. or 2,-hydroxynaphthalene and: substie tution compounds thereof coupling once, such as hydroxynaphthalene sulfonic acids or hydroxynaphthalene carboxylic acids, amino-hydroxynaphthalene sulfonic acids and their derivatives acylated, alkylated or arylated at the nitrogen atom or monoazo dyestuffs which are capable of coupling, such as are Obtained for instance by acid coupling of diazonium compounds. with amino-hydroxynaphthalene monoor -.disulfonic acids.

The dyestuffs obtainable according to this process dye cellulosic fibres such as cotton, linen, ramie, hemp or jute, and fibrous substances from regenerated cellulose, such as staple fibre or rayon, when applied thereonto according to the usual methods for dyestuffs having direct aifinity to these fibres, in greenish to reddish-grey shades. On after-treating the fibres, after the dyeing, with a metal-yielding agent especially valuable dyeings of good fastness to washing are obtained. The said after-treatment can be carried out in the dye-hath or in a new bath by means of copper salts, such as copper sulfate or copper acetate, in a neutral or slightly acid medium. If desired, it.is also possible to use copper compounds which are stable to alkalis, such as are obtained for example by interaction of copper sulfate with sodium tartrate in a sodaalkaline bath.

Dyeings having also excellent fastness properties to washing may be obtained by after-treating the dyeings according to usua1 methods, instead of with the said copper compounds, with other metal-yielding agents, such as for example with chrome, cobalt, manganese or nickel salts. Instead of a single metal-yielding agent, it is adeous to use for the after-treatment mixtures of two or several of the above-mentioned heavy metal salts.

When after-treating the dyeings with metal yielding agents, the shades thereof are only immaterially changed, but considerably improved with respect to the fastness properties to washing and to light.

The dyestuffs claimed herein can, if desired, be converted into the copper complex compound also in substance according to known methods in an acid, neutral or ammoniacal bath by means of copper-yielding agents. With respect thereto it is also possible to treat dyestuffs which are twice metallisable only with one molecule of a copper-yielding agent, to use the incompletely coppered compounds for the dyeing and to aftertreat the dyeings with an agent yielding copper or another metal.

The invention is now described by way of the following examples, without being limited thereto; the parts are by weight.

Example 1 The diazo compound from 19.4 parts of 2- acetylamino--aminobenzoicacid is coupled in a slightly mineral acid solution at room temperature with 31.9 parts of 1-amino-8-hydroxynaph thalene-4t6-disulfonic acid. The finished monoazo dyestufi is treated in a soda alkaline medium with a diazonium compound made from 18 parts of 4 acetylamino-Z-amino -1- methoxybenzene.

The resulting disazo dyestuff is precipitated, dissolved in hot water, saponified by heating with aqueous caustic soda lye and isolated with hydrochloric acid. Then it is dissolved in a sodium carbonate solution, mixed with 13.8 parts of sodium nitrite and, in the cold, '72 parts of concentrated hydrochloric acid is poured thereinto. After complete tetrazotation coupling is effected with 68.6 parts of 2-benzoylamino-8-hydroxynaphthalene-S-sulfonic acid in the presence of an excess of sodium carbonate and the dyestufi is I Example 2 A solution of 31.9 parts of 1-amino-8-hydroxynaphthalene-3:6-disulfonic acid in 250 parts of water is allowed to run in the cold within 2 hours into a diazonium compound made from 182 parts of 5-nitro-2-aminobenzoic acid, 6.9 parts of sodium nitrite and 3 0 parts of concentrated hydrochloric acid. After completion of the formation of the monoazo dyestuff the mixture is made alkaline by means of an excess of sodium carbonate and combined with a diazonium compound obtained in the usual manner from 18 parts of 4- acetylamino 2 amino-l-methoxybenzene. The disazo dyestuif is salted out with a sodium chloride solution, filtered ofi, dissolved in water and reduced with 11.7 parts of sodium sulfide.

Then the aminoacetylaminodisazo dyestuff is off. For the diazotation of the same it is dissolved with sodium carbonate, the resulting sulfur is filtered, the filtrate mixed with 6.9 parts of sodium nitrite and poured in the cold into parts of concentrated hydrochloric acid. After formation of the diazonium compound it is coupled With 18.8 parts of l-hydroxynaphthalene-Z- carboxylic acid in the presence of an excess of sodium carbonate. The trisazo dyestuff thus separated is filtered and saponified by boiling the same with aqueous caustic soda lye. The aminotrisazo dyestufi isolated with hydrochloric acid is dissolved with sodium carbonate, treated with 6.9 parts of sodium nitrite and diazotised by rapidly adding 50 parts of concentrated hydrochloric acid. The diazonium compound is coupled with a solution of 40.3 parts of the monoazo dyestufi, obtained by acid coupling diazotised 1-amino-4- hydroxybenzene-S-carboxylic acid with 2-amino- 5-hydroxynaphthalene-'7-sulfonic acid, and with 40 parts of sodium carbonate in 500 parts of water. The resulting pentakisazo dyestuff is filtered off and dried. It constitutes a dark powder after-treatment with copper salts, possess very good fastness properties in the moist state.

Example 3 51.2 parts of the monoazo dyestuff obtained as described in Example 2 in an acid solution from diazotised 5-nitro-2-aminobenzoic acid and 1- amino-8-hydroxynaphthalene-3 :6-disulfonic acid are combined in the presence of an excess of sodium carbonate with the diazonium compound made in the usual way from 16.8 parts of 5-nitro-2-amino-l-methoxybenzene. The isolated disazo dyestufi is reduced at 35 with a solution of 23.5 parts of sodium sulfide and precipitated by means of hydrochloric acid. For the purpose of tetrazotation the obtained diaminodisazo dyestufi is dissolved in a sodium carbonate solution, the resulting sulfur is filtered, the filtrate mixed with 13.8 parts of sodium nitrite and, in the cold, '72 parts of concentrated hydrochloric acid are poured thereinto. The tetrazotation has completed after some hours.

Now, coupling is effected with 37.6 parts of 1- hydroxynaphthalene-2-carboxylic acid in the presence of parts of sodium carbonate. After some time the precipitated tetrakisazo dyestufi is filtered off and dried. It forms a black powder dissolving in water with a greenish-grey coloration and in concentrated sulfuric acid with a blue coloration and dyeing fibres from natural or regenerated cellulose in grey shades which, on after-treatment with copper, chrome or cobalt salts, are considerably improved with regard to their fastness properties to washing and to water Without impairing the shade.

Example 4 63.1 parts of the diaminodisazo dyestuif 5-nitro-2-aminobenzoic acid H-acid 5-nitro-2- amino-l-methoxybenzene described in Example 3 and reduced are tetrazotised as described above and combined in the presence of 80 parts of sodium carbonate with 80.6 parts of the monoazo dyestufi made by acid coupling diazotised 1- amino-4-hydroxybenzene-3-carboxylic acid and 2-amino-5-hydroxynaphthalene-7-sulfonic acid. The hexakisazo dyestufi is rapidly formed. It is precipitated at 50 C. by means of sodium chlo- 5 ride, filtered offlwashed with dilute brineand fidri'ed' It formsa blackish powder which dissolves in water with a violetish-grey coloration and in concentrated sulfuric acid with a greyishgreen coloration. Fibres from regenerated or natural cellulose are dyed in neutral grey shades which, on after-treatment with copper, .chrome "or cobalt salts, are scarcely changedbut considerably improved with regard to their fastness properties in the moist state.

10 excellent fastness properties.

components; Arr and Ara eachrepresents an aro- -matic radical of the benzene" series -bearing,in *ortho-positiontoan azo group, at least onemember of the group consisting of alkoxy and COOH, and X is a member of the group consisting of H and SOsH, only one X being diiferent from H, which dyestuiis-are dark powders, dissolving in waterwwith a blue to grey coloration and dyeing cellulosic fibres,-when metallised, grey shades of What I claim is:

1. The polyazo dyestufi's which are capable of being metallised, corresponding in the free state to the general formula HO S wherein R1 and R2 each represents a radical of a coupling component selected from the group consisting of aand p-hydroxynaphthalene coupling methoxybenzene 4 carhoxylic acid naphthalene-7-sulfonic acid Tablehade ofthe afte'r i-ammo-B-hydroxynaphtha- Acid coupled dlazonium alkaline coupled diazonium S lene comp und compound ofcompound component; gg zgfi gg iyggg 1 l-amino-S-hydrdxynaphtha- E-acetylamino-Z-aminoi=acetylamino-2-amino-1- 2-hydroxynaphthalenen' 'gr'ey.

lene-izddisulionic acid. benzoic acid. methoxy-benzene'. 1 l-amino-S-hydroxynaphtha- 5-nitro-2-aminobenzoic 5-nitro-2-amino- 1 eth- 2-benzoylamino-8-hydroxynaphreddish grey.

lene-3:6-disulfonic acid. acid. oxybenzene. thalene-fi-sulfonic acid. 3 do rln 5-nitro-2-amino-benzoic 5-nitro- 2-aminobenzoic acid bluish grey.

acid. 2-amino-5-hydroxynap(l11)thalene-7-sulionic acid Cl v 4 do do 4-acetylamino- 2-amino-1- l-hydroxynaphthalene-Z-cargrey.

methoxybenzene. boxylic acid+2-hydroxynaphthalene-fi-sulfonic acid. 5 .do 2-nitro-5-aminobenzoic 2-nitro-5-aminobenzoic l-amino-4-hydroxybenzene-3- Do.

. aci acid. 7 carboxylic acid 2; 7- amino-5-hydroxynaphthalene- V r 7-sulionic acid (acid).

6 d 4-nitro-1'-aminobenzene; 2-acetylamino-5-amino-l- 2-phenylamino-fi-hydroxynaph 'vloletislr-gtey.

methoxybenzene. thalene-7-sulfonic acid. 7 l-amlno-S-hydroxynaph- 2-nitro-5-amino-1-meth- 2-nitro-5-amino-1-meth- 2-hydroxynaphtha1ene-3-car grey.

thailene-eizfi-disulionic oxy-benzene. oxybenzene. boxylic acid. aci 8 do 2-nitro-5amino-l-ethoxydn do Do.

benzene; 9 1-amlno-8-hydroxynaph- 2-nitro-5-amino-1-meth- -nitro-2-amino-l-meth- 2-hydroxynapthalene Do.

thalene-3z6-disulionic acid. oxybenze'ne. oxybenzene. 10 do 5-nitro-2-aminobenzoic 5-nitro-2-amino-1z4-dimeth- 2-hydroxynaphthalene-3-car- 'Do.

aci oxybcnzene. boxylic acid. 11 .d0 2-nitro-5-aminobenzoic 5-nitro-2-aminobenzoic l-amino-4-hydroxybenzene-3- D0.

aci acid. carboxylic acid 2- amino-5-hydroxynaphthalene- 7-sulfonic acid (acid). 12 ..-d0 5-nitro-2-aminobenzoic 5-nitro-2-amino l:4-di-- .do Do. acid. ethoxybenzene. I V 13 .do 2-nitro-5-aminobenzoic 4-acety1ami'no-2-amino-1- 2-benzoylamino-8-hydroxynaphreddish-grey. 1

acid. methoxybenzene. tha1ene6-sulf0nicacid+ lhydroxynaphthalene-2-can' boxylic acid. I 14 5 nitro 2 aminobenzoic 5 nitro 2 amino 1:4- 2 phenyl amino 8 hydroxygrey.

acid diethoxybenzene naphthalene-G-sulfonic acid 15 2 nitro 5 aminobenzoic 2 benzoyl amino 6 hydroxy D0.

' acid naphthalene-S-sulfonic acid 16 d0 do 5-nitro-2-amino -lmethl amino benzene 3 sulfonic violet1sh-grey.

oxy-benzene acid 2 amino 5- v i hydroxy naphthalene 7 sulionic acid (acid) 17 do fin do 1-benzoyl-amino-8-hydroxybluish-grey naphthalene 3:6 disulfonic .acid... 18 fl dn -do 5 nitro 2 amino benzoic D0.

acid l-amino-S- hydroxy naphthalene 3:6 disulfonic acid (acid) 19 .do 5 nltro 2 aminobenzoic 1 hydroxy napthalene 4 sulgrey. aci ionic acid 20 do 5-niti'o f2 amino 1- 2-benzoy1-amino-5-hydroxy- Do.

2. The polyazo dyestuffs which are capable of OE NH:

HOaS- X being metallised, corresponding in the free state to the general formula wherein R1 and R2 mean each a radical of a monoazo dyestufi consisting of an aminonaphbenzene series bearing, in ortho-position to an azo group, at least one member of the group consisting of alkoxy and COOH, and X is a mem-- SOsH 8 4. The polyazo dyestufl which is capable of being metallised, corresponding in the free state to the formula being a dark powder, dissolving in water with a bluish-grey coloration and dyeingvcellulosic ii- 15 bres, when metallised, grey shades of excellent fastness properties.

5. The polyazo dyestuff which is capable of being metallised, corresponding in .the free state to the formula OH NH:

OH on 04111.0 0.11: N=N N=N N=NON=N -NH.C 0.0.11; sour Hols sou: coon Hols ing metallised, corresponding in the free state to the formula being a dark powder, dissolving in water with a violet-greyish coloration and dyeing cellulosic fibres, when metallised, grey shades of excellent 40 fastness properties.

being a dark powder, dissolving in water with a bluish-grey coloration and dyeing cellulosic fl- OH NH: OH

SO;H JJOOH HOaS- bres, when metallised, grey shades of excellent fastness properties.

WERNER BOSSARD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

